Triethylamine → (5,7-Dibromo-adamantan-2-yl)-carbamic acid tert-butyl ester

HRID 1505294Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1505294
[Br:1][C:2]12[CH2:12][CH:6]3[CH2:7][C:8]([Br:11])([CH2:10][CH:4]([CH:5]3C(O)=O)[CH2:3]1)[CH2:9]2.CCN(CC)CC.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=O)C=CC=CC=1.[CH3:40][C:41]([O-:44])([CH3:43])[CH3:42].[K+].[N-:46]=[C:47]=[O:48]>C1(C)C=CC=CC=1.C1COCC1>[C:41]([O:44][C:47](=[O:48])[NH:46][CH:5]1[CH:4]2[CH2:10][C:8]3([Br:11])[CH2:9][C:2]([Br:1])([CH2:12][CH:6]1[CH2:7]3)[CH2:3]2)([CH3:43])([CH3:42])[CH3:40]

Komponenten

8

Edukt 5

HCID 8471TriethylamineHCID 105034IsocyanateHCID 199401P,P-Diphenylphosphinic azideHCID 149770365,7-Dibromoadamantane-2-carboxylic acidHCID 23665647Potassium tert-butoxide

Produkt 1

HCID 16100375(5,7-Dibromo-adamantan-2-yl)-carbamic acid tert-butyl ester

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 1140TolueneLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
85 °C

Versuchsvorschrift

A suspension of the acid 24 (2.00 g, 5.92 mmol) in dry toluene (30 mL) was treated successively with Et3N (1.0 mL, 7.10 mmol) and diphenylphosphoryl azide (DPPA, 1.6 mL, 7.10 mmol). The resulting mixture was stirred at 85° C. for 15 h. To a separated flask containing a solution of t-BuOK (1.35 g, 11.8 mmol) in dry THF (80 mL) at 0° C. was added the isocyanate solution dropwise via a dropping funnel. The resulting reaction mixture was allowed to warm to rt over 30 min, and then it was quenched with water. The THF was removed in vacuo, and the resulting material was diluted with EtOAc. The organic layer was washed with 1N HCl, sat. NaHCO3 and brine, dried (Na2SO4), filtered and concentrated in vacuo. Flash chromatography (SiO2, 95:5 to 8:2, hexanes/EtOAc) afforded 1.20 g (50%, 2 steps) of the title compound as a white powder. 1H NMR (300 MHz, CDCl3) δ 4.68 (bs, 1 H), 3.76 (bs, 1 H), 2.87 (s, 2 H), 2.47-2.13 (m, 10 H), 1.46 (s, 9 H).

Aufarbeitung

  1. customThe resulting reaction mixture
  2. temperatureto warm to rt over 30 min
  3. customit was quenched with water
  4. customThe THF was removed in vacuo
  5. additionthe resulting material was diluted with EtOAc
  6. washThe organic layer was washed with 1N HCl, sat. NaHCO3 and brine
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-c5254ccb20f1456796bf3dbf84dfa7f0
Quelldatensatz
uspto-grants-2015_12
Patentnummer
US09216976B2

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